DOE OSTI2017
This project designed a new type of multi-functional lightweight proppant. The proppant is utilized as the conventional lightweight proppant but also transports microorganisms to coalbed reservoirs. The proppant is coated with a polymer which protects the methanogenic microorganisms and serves as a time-release delivery for methane generation. To produce the multifunctional proppant, we assigned five tasks: 1) culturing methanogenic microbes from natural carbon sources; 2) identifying optimized growth and methanogenesis conditions for the microbial consortia; 3) synthesizing the lightweight ceramic proppant; 4) encapsulating the consortia and proppant; and 5) demonstrating lab scale simulated performance by monitoring in-situ methane generation and hydraulic conductivity. Task 1) To evaluate the feasibility of ex-situ cultivation, natural microbial populations were collected from various hydrocarbon-rich environments and locations characterized by natural methanogenesis. Different rank coals, complex hydrocarbon sources, hydrocarbon seeps, and natural biogenic environments were incorporated in the sampling. Three levels of screening allowed selection of microbial populations, favorable nutrient amendments, sources of the microbial community, and quantification of methane produced from various coal types. Incubation periods of up to 24 weeks were evaluated at 23°C. Headspace concentrations of CH 4 and CO 2 were analyzed by gas chromatography. After a two-week incubation period of the most promising microbes, generated headspace gas concentrations reached 873,400 ppm for methane and 176,370 ppm for carbon dioxide. Task 2) A central composite design (CCD) was used to explore a broad range of operational conditions, examine the effects of the important environmental factors, such as temperature, pH and salt concentration, and query a feasible region of operation to maximize methane production from coal. Coal biogasification was optimal for this consortium at an initial pH value of 5.5, at 30 °C, and at a NaCl concentration 3.7 mg/cm 3 (i.e., 145,165 ppm). Task 3) To create the lightweight ceramic proppant, the kaolinite and iron oxide (Fe 2 O 3 ) mixture were sintered under reducing atmosphere varying partial pressures of oxygen from 1.7×10 -13 atm to 1.8×10-11 atm. The Fe 2 O 3 reduces to FeO and reacts with kaolinite decomposed to mullite to form Fe 2 SiO 4 , FeSiO 3 , and FeAl 2 O 4 . As a result the proppant develops large pores (~100 µm), giving it a low bulk density (1.43 g/cm 3 ), and high porosity (45.2 vol%) at P_(O_2 )of 1.8×10 -11 atm. The proppant sintered at P_(O_2 )of 1.7×10 -13 atm is characterized by smaller pores (26 µm), higher density (1.72 g/cm3) and lower porosity (37.5 vol%). Crush resistance testing at 9,000 psi yields 6.8 wt% fine particles increasing to 17.7 wt% in porous samples. Acid solubility varies from 5.5 wt% loss increasing to 12.9 wt% in porous samples. Task 4 and 5) The microbial consortia obtained from the optimized condition and lightweight proppant were encapsulated by calcium-alginate polymer. The encapsulation system, including microbes and a proppant, was stored at 20°C and 36°C. The sample stored at 36°C generated 7.1×[10] 3 ppm of methane at 670 h, whereas the sample incubated at 20°C generated 1.1×[10] 3 ppm of methane. Benchtop lab-scale bioreactors were constructed and showed with real-time measurements that, as the microbes produced methane, the pH decreased, and hydrogen and carbon dioxide gases were consumed. A calcium ion-selective sensor revealed the release mechanism of the microbes from encapsulation. The calcium ions interconnecting the alginate monomers were disassociated by counter cations such as protons and potassium ions. The counter cations bound to the carboxyl group on the alginate monomer, which thus lost its ionic interactions with the calcium ions, resulting in decomposition of the hydrogel structure. Furthermore, the conductivity was increased to ~700 mD-ft from ~530 mD-ft once the encapsulated sample was applied to the coal pack. The particle size of coal was reduced when the encapsulated sample was added to the coal. The reduced coal size implied that the microbes would consume the hydrocarbon in coal.
01 COAL, LIGNITE, AND PEAT↗